2-(C1-4 Alkoxy)carbonylamino-4-(2&#39;-C1-4 alkoxy-4&#39;-halo-1&#39;,3&#39;,5&#39;-triazinyl-6&#39;-amino)phenylazonaphthalenedisulfonic acids

ABSTRACT

Compounds of the formula ##STR1## in which R 1  is C 1-4  alkyl, 
     Hal is halogen, 
     R 2  is ##STR2##  --SO 2  C 1-4  alkyl, --SO 2  NR 8  R 9  or --NHCOOR 10 , 
     R 3  is hydrogen, C 1-4  alkyl or C 1-4  alkoxy, 
     R 4  is hydrogen or C 1-4  alkyl, 
     R 5  is hydrogen; C 1-4  alkyl; cyclohexyl; cyclohexyl substituted by one to three C 1-4  alkyl groups; phenyl or phenyl substituted by one or two substituents selected from halo, C 1-4  alkyl and C 1-4  alkoxy, 
     R 6  is hydrogen or hydroxy, with the proviso that R 6  is hydrogen when R 2  is --NHCOOR 10 , 
     R 7  is hydrogen, C 1-4  alkyl or C 1-4  alkoxy, 
     each of R 8  and R 9 , independently, is hydrogen, C 1-4  alkyl, C 2-4  hydroxyalkyl, cyclohexyl; or phenyl or phenyl substituted by one or two substituents selected from halo, C 1-4  alkyl, C 1-4  alkoxy, sulfo and carboxy, with the proviso that not more than one of R 8  and R 9  is cyclohexyl, phenyl or substituted phenyl, 
     R 10  is C 1-6  alkyl, the triazinylamino group is in the 4-position when R 2  is --NHCOOR 10  and otherwise is in the 4- or 5-position, 
     m is 1 or 2, 
     n is 0 or 1, and 
     p is 0 or 1, 
     and the molecule contains at least two sulpho groups, and mixtures of such compounds, which compounds are in free acid or salt form and are useful as reactive dyes for dyeing and printing hydroxy group-containing and nitrogen-containing organic substrates such as leather and textile materials consisting of or comprising natural or regenerated cellulose (for example, cotton, viscose and spun rayon) or natural or synthetic polyamides (for example, wool, silk and nylon. The obtained dyeings and prints have notable fastness to light, washing, water, sweat and milling. The combination dyeings obtained when used in combination with other sulfo group-containing reactive dyes are tone-in-tone, resist catalytic fading and exhibit good fastness to light and wet treatments.

The present invention relates to fibre-reactive monoazo compounds, their preparation and use as dyestuffs.

More particularly the present invention provides compounds of formula I, ##STR3## in which

R₁ is C₁₋₄ alkyl,

Hal is halogen,

R₂ is ##STR4##

--SO₂ C₁₋₄ alkyl, --SO₂ NR₈ R₉ or --NHCOOR₁₀, the triazinyl-amino group is bound to the 4- or 5-position, with the proviso that when R₂ is --NHCOOR₁₀ it is bound to the 4-position,

R₃ is hydrogen, C₁₋₄ alkyl or C₁₋₄ alkoxy,

R₄ is hydrogen or C₁₋₄ alkyl,

R₅ is hydrogen; C₁₋₄ alkyl; cyclohexyl optionally substituted by up to three C₁₋₄ alkyl groups; phenyl optionally substituted by up to two substituents selected from the group consisting of halogen, C₁₋₄ alkyl and C₁₋₄ alkoxy,

R₆ is hydrogen or hydroxy, with the proviso that R₆ is other than hydroxy when R₂ is --NHCOOR₁₀,

R₇ is hydrogen, C₁₋₄ alkyl or C₁₋₄ alkoxy,

each of R₈ and R₉, independently, is hydrogen, C₁₋₄ alkyl or C₂₋₄ hydroxyalkyl in which the hydroxy group is in the β-, γ- or δ-position; cyclohexyl; or phenyl optionally substituted by up to two substituents selected from the group consisting of halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, sulpho and carboxy, with the proviso that when one of R₈ and R₉ is cyclohexyl or optionally substituted phenyl, the other has a significance other than cyclohexyl or optionally substituted phenyl,

R₁₀ is C₁₋₆ alkyl,

m is 1 or 2,

n is 0 or 1,

p is 0 or 1, with the provisos:

(a) that n is only 0 and must be 0 when R₂ is --NHCOOR₁₀, and

(b) that the --NHR₅ and the azo groups are ortho to each other in the 1- and 2- or 2- or 1-positions of the naphthalene ring;

and the molecule contains at least two sulpho groups, and mixtures of such compounds, which compounds are in free acid or salt form and are useful as dyestuffs.

By halogen is meant fluorine, chlorine or bromine. On the triazinyl group the preferred halogens are fluorine and chlorine, especially chlorine, and any halogen on a phenyl ring is preferably chlorine or bromine, especially chlorine.

Any alkyl groups or moieties in the molecule are straight chain or branched.

R₁ is preferably C₁₋₃ alkyl, especially methyl.

Any alkyl or alkoxy groups as R₃ preferably contain 1 or 2 carbon atoms, more preferably 1 carbon atom.

R₃ is preferably R₃ ', where R₃ ' is hydrogen, methyl, ethyl, methoxy or ethoxy. More preferably R₃ is R₃ ", where R₃ " is hydrogen, methyl or methoxy, especially hydrogen.

Any alkyl as R₄ is preferably methyl. R₄ is preferably hydrogen or methyl, especially hydrogen.

Any alkyl as R₅ is preferably methyl or ethyl. Any substituted cyclohexyl as R₅ is preferably substituted by up to three methyl groups. Preferred substituted phenyl groups as R₅ are those which are substituted by up to two substituents selected from the group consisting of chlorine, methyl, ethyl, methoxy and ethoxy, especially from the group consisting of chlorine, methyl and methoxy.

R₅ is preferably R₅ ', where R₅ ' is hydrogen, methyl, ethyl, cyclohexyl, phenyl optionally monosubstituted by chlorine, methyl or methoxy. More preferably R₅ is R₅ ", where R₅ " is hydrogen, methyl or phenyl, especially hydrogen.

Any alkyl or alkoxy as R₇ preferably contains 1 or 2 carbon atoms, especially 1 carbon atom.

R₇ is preferably R₇ ', where R₇ ' is hydrogen, methyl or methoxy. More preferably R₇ is R₇ ", where R₇ " is hydrogen or methyl, especially hydrogen.

Any alkyl as R₈ and/or R₉ is preferably methyl or ethyl. Any hydroxyalkyl as R₈ and/or R₉ preferably contains 2 or 3 carbon atoms, with 2-hydroxyethyl being most preferred. Any substituted phenyl as R₈ or R₉ is preferably substituted by up to two substituents selected from chlorine, C₁₋₂ alkyl, C₁₋₂ alkoxy, sulpho and carboxy, especially from the group consisting of methyl and sulpho.

R₈ is preferably R₈ ', where R₈ ' is hydrogen, methyl, ethyl or 2- or 3-hydroxy(C₂₋₃ alkyl); more preferably R₈ is R₈ ", where R₈ " is methyl, ethyl or 2-hydroxyethyl.

R₉ is preferably R₉ ', where R₉ ' is methyl, ethyl, 2- or 3-hydroxy(C₂₋₃ alkyl), cyclohexyl or phenyl optionally substituted by up to two substituents selected from the group consisting of chlorine, C₁₋₂ alkyl, C₁₋₂ alkoxy, sulpho and carboxy; more preferably R₉ is R₉ ", where R₉ " is methyl, ethyl, 2-hydroxyethyl or phenyl optionally substituted by up to two substituents selected from the group consisting of methyl and sulpho.

R₁₀ is preferably C₁₋₄ alkyl, more preferably methyl or ethyl.

R₂ as --SO₂ C₁₋₄ alkyl is preferably --SO₂ C₁₋₂ alkyl.

R₂ is preferably R_(2a) or R_(2b), where R_(2a) is ##STR5## --SO₂ CH₃, --SO₂ C₂ H₅ or --SO₂ NR₈ 'R₉ ' and R_(2b) is --NHCOOC₁₋₄ alkyl. More preferably R_(2a) is R_(2a) ', where R_(2a) ' is ##STR6## --SO₂ CH₃, --SO₂ C₂ H₅ or --SO₂ NR₈ "R₉ ". Most preferably R_(2a) is R_(2a) ", where R_(2a) " is ##STR7##

R_(2b) is preferably R_(2b) ', where R_(2b) ' is --NHCOOCH₃ or --NHCOOC₂ H₅.

Preferably the compounds of formula I contain 2 sulpho groups. When R₆ is hydroxy m is preferably 1.

In the naphthalene ring the substituents are preferably as follows:

(a) when n is 1

with the --NHR₅ group in the 1-position and when R₆ is hydrogen and when m is 1, the sulpho group is in the 4-position and when m is 2 the sulpho groups are in the 3,6-, 3,8- or 4,6-, preferably the 3,6- or 4,6-, positions; with the --NHR₅ group in the 2-position and when R₆ is hydrogen and when m is 1 the sulpho group is in the 5-, 6- or 7-position and when m is 2 the sulpho groups are in the 3,6- or 5,7-positions;

with the --NHR₅ group in the 2-position and R₆ is hydroxy (preferably in the 8-position) and m is 1, the sulpho group is in the 6-position.

(b) when n is 0 and m is 2

with the azo group in the 1-position the sulpho groups are in the 3,6-, 3,8-, 4,6- or 4,8-positions; with the azo group in the 2-position the sulpho groups are in the 3,6-, 4,8-, 5,7- or 6,8-positions.

The --NHR₅ group is preferably in the 2-position of the naphthalene ring.

Preferred compounds of formula I are

(i) those in which n is 1, R₂ is R_(2a), Hal is flourine or chlorine and the compound contains 2 sulpho groups;

(ii) those of (i) in which R₃ is R₃ " and R₄ is hydrogen or methyl;

(iii) those of (i) or (ii) in which R₅ is R₅ ';

(iv) those of formula Ia ##STR8## in which m is as defined above, with the proviso that m is 1 when R₆ is hydroxy;

(v) those of (iv) in which R₅ " is hydrogen;

(vi) those of (iv) or (v) in which R_(2a) ' is R_(2a) ", and

(vii) those of (iv), (v) or (vi) in which R₁ is C₁₋₃ alkyl, especially methyl.

(viii) those of formula Ib ##STR9## in which Hal' is fluorine or chlorine;

(ix) those of (viii) in which R_(2b) is R_(2b) ', and

(x) those of (viii) or (ix) in which R₃ " and R₄ are both hydrogen, Hal' is chlorine and R₁ is C₁₋₃ alkyl, especially methyl.

The present invention further provides a process for the production of compounds of formula I comprising (a) coupling the diazonium derivative of a compound of formula II, ##STR10## in which

R₂ ' is R₂ is defined above with the exception of the group --NHCOOR₁₀,

X is --NO₂ or --NR₄ Z₁ and is in the 4- or 5-position,

Z₁ is a protecting group or is a radical of formula (a) or (b) ##STR11## or a mixture thereof, with a compound of formula III ##STR12## or a mixture thereof, and when Z₁ is (a) condensing the product with a compound R₁ OH and when X is nitro reducing the same or Z₁ is a protecting group, splitting off such group and reacting the --NH₂ or --NHR₄ group either with cyanuric halide followed by reacting the product with a compound R₁ OH or with a compound of formula (c) ##STR13## to obtain a compound of formula I in which n is 1, or (b) reacting a compound of formula IV ##STR14## or a mixture thereof, either, with cyanuric halide followed by reacting with a compound R₁ OH, or, with a compound of formula (c), to obtain a compound of formula I in which n is 0.

In processes (a) and (b) it is preferred to employ a compound of formula (c) rather than reacting with cyanuric halide and then with a compound R₁ OH. The condensation reactions with cyanuric halide and R₁ OH or with the compound of formula (c) are carried out in accordance with known methods. The compounds of formula IV are obtained by coupling the diazonium derivative of a compound of formula V ##STR15## with a compound of formula VI ##STR16##

The coupling reaction is carried out in accordance with known methods, suitably in acid medium, preferably in a medium having a pH in the range of from 2.0 to 4.5.

The compounds of formula I may be isolated in accordance with known methods. It will be appreciated that, depending on the reaction and isolation conditions, the compounds of formula I may be obtained in the salt form whereby the neutralizing cation may be any of those non-chromophoric cations conventional for the salt form of reactive dyestuffs. Preferred cations are lithium, sodium and potassium, especially sodium.

The starting materials of formulae II, III, V and VI are either known or may be prepared in accordance with known methods from available starting materials.

The compounds of formula I and mixtures thereof are useful as reactive dyestuffs for dyeing or printing hydroxy group-containing or nitrogen-containing organic substrates. Preferred substrates are leather and textile materials consisting of or comprising natural or regenerated cellulose such as cotton, viscose and spun rayon, natural or synthetic polyamides such as wool, silk and/or nylon. The most preferred substrates are those textile substrates consisting of or containing wool.

The compounds of formula I, in dyebaths or with printing pastes, may be employed in accordance with conventional dyeing and printing methods for reactive dyes. For polyamide substrates it is preferred to employ exhaust dyeing methods.

The dyeings and prints obtained have notable wet-fastness (wash-, water-, sweat- and milling-fastness) and light-fastness.

The compounds of the invention are also useful as combination dyes, especially for use with other sulpho group-containing reactive dyestuffs. The combination dyeings obtained are tone-in-tone and exhibit the usual desired properties of combination dyeings, e.g. no catalytic fading, good light- and wet-fastnesses, etc.

The following Examples further serve to illustrate the invention. In the Examples all parts are by weight and the temperatures are in degrees Centigrade.

EXAMPLE 1

40.6 Parts 1-amino-2-p-toluenesulfonyl-4-(2'-chloro-4'-methoxy-1,3,5-triazinyl)aminobenzene are reacted with 25 parts 30% hydrochloric acid in 600 parts water/acetone mixture followed by diazotization with 7 parts sodium nitrite in 50 parts water. The reaction mixture is diluted with 900 parts water, stirred for 1 hour at 0°-5° and the excess nitrous acid is decomposed with aminosulphonic acid.

The diazo suspension is added dropwise to a solution of 30.3 parts 2-aminonaphthalene-3,6-disulphonic acid in 600 parts water at 0°-5° whilst the pH is kept at 4.0-4.5 by adding 75 parts sodium acetate. The suspension is diluted with 600 parts acetone and the temperature is allowed to rise to 20°, the pH is adjusted to 8 and the product is filtered off. The product which, in free acid form is of the formula ##STR17## is obtained in sodium salt form and dyes polyamides, especially wool, in scarlet-red shades. The dyeings have good light- and wet-fastnesses.

In the following Table further dyes which may be prepared in analogy with the procedure of Example 1 are given. The compounds correspond to the general formula ##STR18##

In Table 1 the symbol K denotes the following naphthalene groups (K₁) to (K₁₅) ##STR19##

The dyeings on wool have the shades indicated in the last column of Table 1, whereby a=orange, b=scarlet-red, c=red and d=bordeaux red.

                                      TABLE 1                                      __________________________________________________________________________     Ex.                          position                                                                              shade on                                   No.                                                                               K  R.sub.2      Hal                                                                               R.sub.1                                                                               of NHZ wool                                       __________________________________________________________________________     2  K.sub.1                                                                            ##STR20##   Cl CH.sub.3                                                                              4      b                                          3  K.sub.1                                                                           "            Cl "      5      b                                          4  K.sub.2                                                                           "            Cl "      4      b                                          5  K.sub.3                                                                           "            F  "      5      b                                          6  K.sub.3                                                                           "            Cl C.sub.2 H.sub.5                                                                       5      b                                          7  K.sub.4                                                                           "            Cl CH.sub.3                                                                              5      a                                          8  K.sub.5                                                                            ##STR21##   Cl "      5      c                                          9  K.sub.5                                                                            ##STR22##   Cl CH.sub.3                                                                              5      c                                          10 K.sub.4                                                                            ##STR23##   Cl "      5      a                                          11 K.sub.1                                                                           "            Cl "      5      b                                          12 K.sub.2                                                                           "            Cl "      4      b                                          13 K.sub.3                                                                           "            Cl "      5      b                                          14 K.sub.4                                                                           "            F  "      5      b                                          15 K.sub.5                                                                           "            Cl "      5      c                                          16 K.sub.5                                                                           "            Cl CH(CH.sub.3).sub.2                                                                    5      c                                          17 K.sub.10                                                                          "            Cl CH.sub.3                                                                              5      d                                          18 K.sub.7                                                                            ##STR24##   Cl "      5      c                                          19 K.sub.10                                                                          "            Cl "      5      d                                          20 K.sub.9                                                                           "            Cl "      4      c                                          21 K.sub.12                                                                           ##STR25##   F  "      5      b                                          22 K.sub.13                                                                          "            Cl "      5      b                                          23 K.sub.13                                                                           ##STR26##   Cl CH.sub.3                                                                              5      b                                          24 K.sub.12                                                                          "            Cl "      4      b                                          25 K.sub.14                                                                          "            Cl "      5      b                                          26 K.sub.12                                                                           SO.sub.2 CH.sub.3                                                                          Cl "      4      b                                          27 K.sub.12                                                                          "            Cl "      5      b                                          28 K.sub.13                                                                          "            Cl C.sub.2 H.sub.5                                                                       5      b                                          29 K.sub.15                                                                          SO.sub.2 C.sub.2 H.sub.5                                                                    Cl CH.sub.3                                                                              5      b                                          30 K.sub.12                                                                           ##STR27##   Cl "      5      b                                          31 K.sub.12                                                                           ##STR28##   Cl "      5      b                                          32 K.sub.13                                                                          SO.sub.2 C.sub.4 H.sub.9 (n)                                                                Cl "      5      b                                          33 K.sub.14                                                                          SO.sub.2 CH.sub.3                                                                           Cl "      4      b                                          34 K.sub.15                                                                           ##STR29##   Cl "      5      b                                          35 K.sub.13                                                                          SO.sub.2 N(CH.sub.3).sub.2                                                                  Cl "      5      b                                          36 K.sub.12                                                                          SO.sub.2 NHCH.sub.3                                                                         Cl "      5      b                                          37 K.sub.12                                                                          SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                           Cl "      4      b                                          38 K.sub.12                                                                          SO.sub.2 N(CH.sub.2 CH.sub.2 OH).sub. 2                                                     Cl "      5      b                                          39 K.sub.12                                                                           ##STR30##   Cl "      5      b                                          40 K.sub.13                                                                           ##STR31##   Cl "      5      b                                          41 K.sub.13                                                                           ##STR32##   Cl "      5      b                                          42 K.sub.13                                                                           ##STR33##   Cl CH.sub.3                                                                              4      b                                          43 K.sub.1                                                                            ##STR34##   Cl C.sub.2 H.sub.5                                                                       5      b                                          44 K.sub.5                                                                           "            Cl CH.sub.3                                                                              5      c                                          45 K.sub.4                                                                           "            Cl "      5      b                                          46 K.sub.1                                                                            ##STR35##   Cl C.sub.2 H.sub.5                                                                       5      b                                          __________________________________________________________________________

EXAMPLE 47

30.3 Parts 2-aminonaphthalene-6,8-disulphonic acid are stirred in 180 parts water, 100 parts ice and 14 parts 30% hydrochloric acid and are diazotized within 30 minutes at 0°-5° by the addition of 6.9 parts sodium nitrite in 25 parts water. After stirring for a further 15 minutes, the reaction is complete.

18.4 Parts 1-aminobenzene-3-carbamic acid ethyl ester are stirred in 150 parts water. The diazo suspension is added within 30 minutes to the solution whilst the pH is kept between 4 and 4.5 by adding 20 parts 30%-sodium-hydroxide solution. The dissolved dye is precipitated by the addition of 85 parts sodium chloride and is then filtered. The paste obtained is dissolved at pH 6 in 1000 parts water. 18 parts 2,4-dichloro-6-methoxy-1,3,5-triazine are added within 15 minutes at room temperature whilst the pH is kept at 5.5 to 6.0 by adding 30 parts 20% sodium carbonate solution. After condensation is complete, 100 parts sodium chloride are added and the precipitated dye is filtered. The product which, in free acid form is of the formula ##STR36## is obtained in sodium salt form. The dye gives golden-yellow dyeings on polyamides such as wool, which dyeings have good light- and wet-fastnesses.

In analogy with the procedure described in Example 47, the dyes of Table 2 which correspond to the general formula ##STR37## may be prepared.

In the Table the dye shade on wool is given in the last column whereby e=yellow and f=golden-yellow.

                  TABLE 2                                                          ______________________________________                                         Ex.  amine containing                 shade on                                 No.  D             R.sub.10 R.sub.1   wool                                     ______________________________________                                         48   2-aminonaphthalene-                                                                          C.sub.2 H.sub.5                                                                         --CH(CH.sub.3).sub.2                                                                     f                                             6,8-disulfonic acid                                                       49   2-aminonaphthalene-                                                                          CH.sub.3 CH.sub.3  f                                             6,8-disulfonic acid                                                       59   2-aminonaphthalene-                                                                          C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                          f                                             6,8-disulfonic acid                                                       51   2-aminonaphthalene-                                                                          "        CH.sub.3  f                                             4,8-disulfonic acid                                                       52   2-aminonaphthalene-                                                                          "        --CH.sub.2 CH.sub.2 CH.sub.3                                                             f                                             4,8-disulfonic acid                                                       53   2-aminonaphthalene-                                                                          C.sub.4 H.sub.9 (n)                                                                     CH.sub.3  f                                             4,8-disulfonic acid                                                       54   2-aminonaphthalene-                                                                          CH.sub.3 "         f                                             5,7-disulfonic acid                                                       55   2-aminonaphthalene-                                                                          C.sub.2 H.sub.5                                                                         "         f                                             5,7-disulfonic acid                                                       56   2-aminonaphthalene-                                                                          "        --CH(CH.sub.3).sub.2                                                                     f                                             5,7-disulfonic acid                                                       57   1-aminonaphthalene-                                                                          "        CH.sub.3  e                                             3,6-disulfonic acid                                                       58   1-aminonaphthalene-                                                                          "        "         e                                             4,6-disulfonic acid                                                       59   1-aminonaphthalene-                                                                          "        "         e                                             4,8-disulfonic acid                                                       ______________________________________                                    

DYEING EXAMPLE A

1 Part of the dye of Example 1 is dissolved in 250 parts demineralized water. 5 parts unchlorinated wool cable yarn are added to the dyebath and the temperature is adjusted to 40°. 5 parts calcinated Glauber's salt, 1.5 parts glacial acetic acid and 1 part conventional levelling agent are added to the bath; the bath is heated to the boil within 90 minutes and kept at the boil for 60 minutes. During dyeing evaporated water is replaced every 15 minutes. The dyed substrate is washed in running hot water, then in running cold water (each for c. 3 minutes) and dried at approximately 70°. A scarlet-red dyeing having good light- and wet-fastnesses is obtained. Synthetic polyamide may be dyed in similar manner. Similarly, the dyes of Examples 2 to 59 may be employed to dye wool in accordance with the method described above. 

What we claim is:
 1. A compound of the formula ##STR38## or a salt thereof each cation of which is non-chromophoric, wherein R₁ is C₁₋₄ alkyl,R₃ " is hydrogen, methyl or methoxy, R₄ is hydrogen or C₁₋₄ alkyl, R₁₀ ' is C₁₋₄ alkyl, and Hal' is fluoro or chloro.
 2. A compound according to claim 1, or a salt thereof each cation of which is non-chromophoric, wherein R₁₀ ' is methyl or ethyl.
 3. A compound according to claim 1, or a salt thereof each cation of which is non-chromophoric, whereinR₁ is C₁₋₃ alkyl, R₃ " is hydrogen, R₄ is hydrogen, and Hal' is chloro.
 4. A compound according to claim 1, or a salt thereof each cation of which is non-chromophoric, wherein R₁ is methyl.
 5. A lithium, sodium or potassium salt of a compound according to claim
 1. 6. The sodium salt of the compound according to claim 4 having the formula ##STR39## 